EP0267562B1 - Préparation de liant pour peinture diluable dans l'eau et séchable à l'air - Google Patents

Préparation de liant pour peinture diluable dans l'eau et séchable à l'air Download PDF

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Publication number
EP0267562B1
EP0267562B1 EP19870116502 EP87116502A EP0267562B1 EP 0267562 B1 EP0267562 B1 EP 0267562B1 EP 19870116502 EP19870116502 EP 19870116502 EP 87116502 A EP87116502 A EP 87116502A EP 0267562 B1 EP0267562 B1 EP 0267562B1
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Prior art keywords
weight
resin
monomers
water
acid
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EP19870116502
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German (de)
English (en)
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EP0267562A3 (en
EP0267562A2 (fr
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Bertram Dr. Zückert
Gerfried Dr. Klintschar
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Solutia Austria GmbH
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Vianova Resins AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids

Definitions

  • the invention relates to a process for producing water-thinnable air-drying lacquer binders based on vinyl- or acrylic-modified alkyd resin emulsions and their use in oxidatively air-drying, water-thinnable lacquers at temperatures up to 100 degrees C.
  • No. 4,116,903 describes copolymer dispersions in which water-soluble alkyd resins based on isophthalic acid and trimellitic acid are used as emulsifier components.
  • the stability of the dispersions produced in this way is also not sufficient in this case.
  • the progressive hydrolysis of the alkyd resin component leads, on the one hand, to loss of the emulsifying or. Dispersing effect for polymer content and pigments, and on the other hand through degradation of the alkyd resin molecules to a decrease in drying speed and film quality.
  • alkyd resin emulsions are known in which the alkyd resins acting as emulsifiers are built up in such a way that the carboxyl groups effective for salt formation are introduced by copolymerization of methacrylic acid with part of the fatty acids used for alkyd resin formation will. Varnishes on this basis are well suited for many purposes in which the required shelf life is about 1 year. After storage periods of more than one year, however, the same disadvantages as are known from isophthalic or trimellitic acid alkyd resins are evident. Because the so-called paints, but also for automotive refinish and wood glazes require a shelf life of 2 to 3 years, it was not possible to achieve a breakthrough with these types of binders either.
  • these products Due to their high unsaponifiable polymer content, these products show a significantly improved storage stability, without the fact that the thermoplasticity that is otherwise customary with polymers occurs when the material is well dried. As expected, the products show a slight yellowing of the aged films. Surprisingly, the products show good pigment wetting and good gloss even without the use of polyethylene glycols in the alkyd resin formulation. Of course, the use of this component is not excluded. In special cases this can facilitate the formulation of the lacquer, eg when using "difficult" pigments.
  • the alkyd resins, urethane alkyd resins or epoxy resin esters used as emulsifier resins for the process according to the invention are water-soluble on their carboxyl groups through at least partial salt formation with ammonia or organic amines. It should be noted that this water solubility does not necessarily lead to clear solutions. As is known to the person skilled in the art, the products are present in these solutions as larger resin micelles, so that the solution can also have an opaque or even cloudy appearance.
  • the common feature of the emulsifier resins is that they contain free acid groups corresponding to an acid number of 35 to 70 mg KOH / g, at least 80% of these acid groups being derived from methacrylic acid residues which were grafted onto at least some of the unsaturated fatty acids used in a separate reaction step. Otherwise, the alkyd resins, urethane alkyd resins and epoxy resin esters show the structure known from the literature.
  • the content of drying and / or semi-drying fatty acids in these resins is between 40 and 70% by weight.
  • a proportion of 10 to 40% by weight, based on the resin weight, of these fatty acids is introduced in the form of the fatty acid-methacrylic acid copolymer.
  • the alkyd resins used according to the invention are furthermore particularly characterized in that they contain from 10 to 25% by weight of polyalcohols with 2 to 6 hydroxyl groups, 10 to 15% by weight of aromatic and / or aliphatic dicarboxylic acids, 0 to 10% by weight .-% cyclic and / or polycyclic monocarboxylic acids and 0 to 10 wt .-% of a polyethylene glycol.
  • the products have an intrinsic viscosity between 7 and 14 ml / g, measured in chloroform at 20 degrees Celsius.
  • the urethane alkyd resins contain 10 to 25% by weight of polyalcohols with 2 to 6 hydroxyl groups, 0 to 10% by weight of aromatic and / or aliphatic dicarboxylic acids, 5 to 15% by weight of aromatic and / or aliphatic and / or cycloaliphatic Diisocyanates, 0 to 10% by weight of cyclic and / or polycyclic monocarboxylic acids and 0 to 10% by weight of a polyethylene glycol. Your intrinsic viscosity is between 8 and 14 ml / g (CHCl3 / 20 degrees C).
  • the epoxy resin esters contain 15 to 35% by weight of epoxy resins, preferably the commercially available bisphenol A diepoxy resins, with an epoxy equivalent weight between approximately 180 and approximately 500, and 0 to 10% by weight. % of a polyethylene glycol.
  • the intrinsic viscosity is 8 to 14 ml / g (CHCl3 / 20 degrees C).
  • unsaturated fatty acids with an iodine number above 135 (preferably 160-200) and with a predominantly isolated position of the double bonds are used.
  • Suitable are, inter alia, linseed oil fatty acid, safflower oil fatty acid and the fatty acids of hemp, lallemantia, perilla and stilling oil, optionally in a mixture with up to 25% by weight. on dehydrated castor fatty acid or a similar conjugated fatty acid produced by isomerization.
  • the fatty acid copolymers are composed of 30 to 50% by weight of the abovementioned fatty acids, 10 to 25% by weight of methacrylic acid and 30 to 55% by weight of other monomers which, apart from the CC double bond, have no further functional groups. where the sum of the percentages must be 100.
  • Monomers which are used in addition to methacrylic acid are preferably (meth) acrylic compounds and aromatic vinyl compounds, in particular those which form gasoline-soluble polymers with a glass transition point (Tg) of 20 to 60 degrees C.
  • Vinyltoluene is used to adjust the optimal Tg range of the copolymer or the resulting film hardness.
  • monomers which form gasoline-insoluble polymers, such as methyl methacrylate or styrene, can also be used.
  • the graft copolymerization is carried out in such a way that the majority of the fatty acid, if appropriate in the presence of small amounts of inert solvents, is heated to 110-150 ° C. and the mixture of monomers is metered in with a suitable initiator and the remaining fatty acid over the course of a few hours. The reaction mixture is then kept at the reaction temperature until a residue determination gives a polymerization conversion of over 95%.
  • Suitable initiators include di-tert-butyl peroxide, tert-butyl perbenzoate and cumene hydroperoxide.
  • the fatty acid-methacrylic acid graft copolymers prepared in this way are processed together with further fatty acids to form water-soluble alkyd resins, urethane alkyd resins or epoxy resin esters.
  • Vegetable and animal fatty acids with an iodine number above 120 can be used as fatty acids in this stage, with a part of the double bonds preferably being in the conjugated position.
  • Suitable polyols and dicarboxylic acids for the production of the alkyd resins are all products which are also used for the production of conventional alkyd resins.
  • Trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol are preferably used as polyols and ortho- or isophthalic acid and adipic acid as dicarboxylic acids.
  • Cyclic or polycyclic monocarboxylic acids, such as resin acids or benzoic acid, can also be used to regulate the film hardness.
  • proportions of up to 10% by weight of polyethylene glycols with a molecular weight of 1000 to 3000 can also be incorporated.
  • the esterification can be carried out by heating all components together.
  • high-melting raw materials such as pentaerythritol and isophthalic acid
  • the esterification is then carried out so far that the final value of the acid number corresponds to approximately 90% of the concentration of the carboxyl groups of methacrylic acid.
  • alkyd resin components according to the invention are therefore far superior in hydrolysis resistance to the previously known water-dilutable alkyd resins based on o-phthalic acid, isophthalic acid or trimellitic acid.
  • the unmodified fatty acids, optionally the dicarboxylic acids and the fatty acid-methacrylic acid copolymer are first esterified with the polyols in the same way as in the production of the alkyd resins.
  • the resulting oligoester is then reacted with the isocyanates in the presence of inert solvents until the NCO content has dropped below 0.1% and the desired intrinsic viscosity has been reached.
  • the unmodified fatty acids and the preferably used amine or alkali hydroxide catalysts are placed in the reactor. At approx. 150 degrees C, the epoxy resin is added in portions and the mixture to 180 degrees C. heated. The fatty acid copolymer is then added and the esterification is continued at 170 to 200 ° C. until the desired acid number or the intrinsic viscosity is reached.
  • the water-dilutable alkyd resins, urethane alkyd resins or epoxy resin esters thus produced serve as emulsifier resins for the preparation of the copolymer emulsions.
  • they are freed of inert solvents under vacuum and prediluted with part of the water-compatible co-solvents required for the emulsion preparation.
  • ammonia, organic amines or alkali metal hydroxides, in the amount necessary to achieve perfect water dilutability, and all the water are added, and an aqueous solution or emulsion is prepared by stirring at 60 to 80 degrees C.
  • the mixture of the monomers selected for the emulsion polymerization with the remaining water-compatible co-solvent and the initiator is then metered in uniformly over the course of a few hours.
  • the reaction temperature is then held until a polymerisation conversion of over 95% results from residue determinations.
  • part of the emulsifier resin is slowly metered in together with the monomer mixture.
  • emulsifier resin up to 20%, based on the binder solid, of water-insoluble alkyd resins, urethane alkyd resins, epoxy resin esters or, optionally prepolymerized, drying oils and the like.
  • emulsifier resin up to 20%, based on the binder solid, of water-insoluble alkyd resins, urethane alkyd resins, epoxy resin esters or, optionally prepolymerized, drying oils and the like.
  • Such monomers for the emulsion polymerization are essentially those vinyl and / or (meth) acrylic compounds used which carry no further reactive group besides the CC double bond.
  • examples of such monomers are the acrylic acid alkanol esters, preferably of butanol or its isomers or higher homologues, the methacrylic acid esters of methanol, ethanol, the propanols and butanols, and aromatic vinyl compounds such as styrene, alpha-methylstyrene, vinyltoluene and others.
  • functional monomers bearing functional groups can also be used.
  • up to 10%, based on the total binder, of OH-functional monomers, such as 2-hydroxyethyl methacrylate, and up to 2% of acidic monomers, such as methacrylic acid can also be used.
  • Azo compounds such as azo-isobutyrodinitrile or azo-isovalerodinitrile have proven to be the best initiators.
  • organic and inorganic peroxides such as dibenzoyl peroxide or potassium peroxydisulfate, can also be used.
  • Particularly suitable organic, water-compatible co-solvents are the methyl, ethyl and butyl ethers of ethylene glycol, diethylene glycol, 1,2-propylene glycol and dipropylene glycol. In some cases, only water-compatible solvents such as n- and iso-butanol can be used. The total content of organic solvents in the finished emulsion should not exceed 10%.
  • Triethylamine dimethylethanolamine, KOH, NaOH and LiOH are suitable.
  • the binders produced according to the invention can be pigmented or unpigmented in a conventional manner Form, if necessary after the addition of customary paint auxiliaries, by brushing, flooding, spraying or dipping.
  • the paints are dried at room temperature or by forced air drying at temperatures up to 100 degrees C. If the binders are built up appropriately and crosslinking agents are used, the binders can also be used for stoving enamels.
  • a copolymer is prepared from 41 parts of linseed oil fatty acid, 22 parts of isobutyl methacrylate, 10 parts of n-butyl methacrylate, 10 parts of vinyl toluene and 17 parts of methacrylic acid in the presence of 10 parts of xylene.
  • the copolymer has an acid number of 185 mg KOH / g and an intrinsic viscosity (DMF) of 5.1.
  • alkyd resins are produced in the following way: In a suitable reaction vessel, the components of part 1 are esterified at 230 ° C. until a clear melt has formed. After another hour, part 2 is added and the reaction is carried out at 200 degrees C until the specified end values are reached.
  • Part 1 and part 2 are esterified as described in (a) until the acid number corresponds to approximately 95% of the methacrylic acid carboxyl groups.
  • the resulting oligoesters are dissolved in as much toluene that the reaction product with the diisocyanate has a solids content of 60%. After heating to 60 degrees C, the isocyanate is added and the temperature is increased to 100 degrees C after the addition has ended. The reaction is then continued until an NCO value of 0 and the desired intrinsic viscosity are reached.
  • the fatty acids specified in part 1 of the table and the catalyst are heated to 150 ° C. in a suitable reaction vessel under inert gas.
  • the epoxy resin is added in portions within 60 minutes and then the fatty acid-methacrylic acid copolymer (part 2) is added at 180 ° C.
  • the batch is esterified at 200 degrees C until the end values are reached.
  • the emulsifier resins A1 - A5, U1 - U3 or E1 and E2 are freed from the solvent present by vacuum distillation. Then the batch is mixed with 10% of its weight with ethylene glycol monobutyl ether (BUGL).
  • BUGL ethylene glycol monobutyl ether
  • the dehydrated castor oil (DCO) used in Example 5 is emulsified as an additional component with the first part of the alkyd resin with the water-ammonia mixture.
  • Comparative example 3 corresponds to example 1 according to the invention, the emulsifier resin A1 being replaced by the alkyd resin used in example 1 of US Pat. No. 4,116,903 (example D).
  • the change in the acid number, the pH value and the intrinsic viscosity number is tested after the 30% emulsions have been stored for 96 hours at 70 degrees C.
  • the emulsions are mixed with 2% of a commercially available water-compatible cobalt-siccative solution and 1% of a commercially available skin-preventing agent based on oxime and diluted with deionized water to such an extent that a flowable clear lacquer with a solids content of between approximately 35 and 40% is formed.
  • the lacquers are applied to glass strips after a ripening time of 24 hours in a layer thickness which corresponds to a dry film thickness of 30 to 40 ⁇ m.
  • the drying process is tracked with an appropriate device (e.g. drying recorder).
  • the emulsions were mixed with desiccant and skin-preventing agent and ground on a bead mill with titanium dioxide (rutile type) in a pigment / binder ratio of 0.8: 1.
  • the lacquers applied to glass plates are tested in a dry film thickness of 30 to 40 ⁇ m with regard to drying, hardness, gloss and water resistance. The drying was tested as in (B).
  • the hardness was tested according to DIN 53 157 (K ⁇ NIG). The specified values are seconds.
  • the water resistance is tested by storing the films dried for 1 week at room temperature in water at 20 degrees C for 24 hours (E: film softens, regenerates after a few hours).
  • a red machine paint is produced and tested using SICOMIN-Rot L 3330 S (BASF AG) in a pigment / binder ratio of 0.5: 1 and according to the information given under (C).
  • a corrosion protection varnish which was produced in the manner described above and according to the following recipe, is tested. 220 parts emulsion about 45% according to the example 100 parts iron oxide red 50 parts calcium carbonate 50 parts of zinc phosphate 2 parts of siccative mixture 1 teaspoon of skin preventing agent 1 tsp anti-settling agent 1 tsp defoamer The paint is applied 24 hours after production on glass plates or for the salt spray test (according to ASTM B-117-64) on degreased steel sheet.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Graft Or Block Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)

Claims (9)

  1. Procédé de préparation de liants pour peintures diluables à l'eau et séchant à l'air à base d'émulsions de résines alkydes vinyl- et/ou (méth)acrylmodifiées, caractérisé en ce que l'on polymérise jusqu'à un rendement de polymérisation d'au moins 95% en présence d'un amorceur radicalaire
    20 à 70% en poids   d'un mélange de monomères vinyl- et/ou (méth)acryliques qui ne portent sensiblement pas de groupes fonctionnels à côté de la double liaison C-C, entre 60 et 80°C en présence d'une solution ou émulsion aqueuse contenant éventuellement de faibles quantités de solvants auxiliaires de
    30 à 80% en poids   d'une résine alkyde et/ou d'une résine uréthanne-alkyde et/ou d'un ester de résine époxyde, hydrosolubles après neutralisation au moins partielle, qui présentent une teneur totale en acides gras de 40 à 70% en poids, parmi lesquels 10 à 40% en poids, par rapport à la résine émulsifiante, sont greffés avec l'acide méthacrylique et d'autres monomères, et dont les groupes carboxyle libres, correspondant à un indice d'acide de 35 à 70 mg de KOH/g proviennent à raison d'au moins 80% d'unités d'acide méthacrylique, qui, en même temps que d'autres monomères vinyl-et/ou (méth)acryliques qui ne portent aucun autre groupe fonctionnel à côté de la double liaison C-C, ont été greffées avant la formation de la résine sur une partie des acides gras insaturés, ainsi que
    jusqu'à 20% en poids   d'une résine alkyde et/ou d'une résine uréthanne-alkyde et/ou d'un ester de résine époxyde et/ou d'une huile siccative éventuellement prépolymérisée, insolubles dans l'eau, émulsifiés dans la résine hydrosoluble
    la somme des pourcentages pour la composition devant être à chaque fois égale à 100.
  2. Procédé selon la revendication 1, caractérisé en ce que le copolymère acide gras-acide méthacrylique consiste en 30 à 50% en poids d'acides gras ayant un indice d'iode supérieur à 135, de préférence de 160 à 200, et une fraction prépondérante de doubles liaisons multiples isolées, 10 à 25% en poids d'acide méthacrylique et 30 à 55% en poids d'autres monomères, de préférence des composés (méth)acryliques et/ou des composés vinyliques aromatiques, en particulier ceux qui forment des polymères solubles dans l'essence présentant une température de transition vitreuse de 20 à 60°C.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que les résines alkydes utilisées comme résines émulsifiantes consistent, à côté de la fraction acide gras et de la fraction polymérique greffée, en 10 à 25% en poids de polyalcools ayant 2 à 6 groupes hydroxyle, 10 à 15% en poids de diacides carboxyliques aromatiques et/ou aliphatiques, jusqu'à 10% en poids de monoacides carboxyliques (poly)cycliques et jusqu'à 10% en poids d'un polyéthylèneglycol ayant un poids moléculaire compris entre 1000 et 3000 et présentent un indice de viscosité limite, mesuré dans le chloroforme à 20°C, de 7 à 14 ml/g.
  4. Procédé selon les revendications 1 et 2, caractérisé en ce que les résines uréthanne-alkydes utilisées comme résines émulsifiantes consistent, à côté de la fraction acide gras et de la fraction polymérique greffée, en 10 à 25% en poids de polyalcools ayant 2 à 6 groupes hydroxyle, 5 à 15% en poids de diisocyanates aromatiques et/ou aliphatiques et/ou cycloaliphatiques, jusqu'à 10% en poids de diacides carboxyliques aromatiques et/ou aliphatiques, jusqu'à 10% en poids de monoacides carboxyliques (poly)cycliques et jusqu'à 10% en poids d'un polyéthylèneglycol ayant un poids moléculaire compris entre 1000 et 3000 et présentent un indice de viscosité limite, mesuré dans le chloroforme à 20°C, de 8 à 14 ml/g.
  5. Procédé selon les revendications 1 et 2, caractérisé en ce que les esters de résines époxydes utilisés comme résine émulsifiante consistent, à côté de la fraction acide gras et de la fraction polymérique greffée, en 15 à 35% en poids d'une résine époxyde, de préférence une résine diépoxyde de bisphénol A, ayant un poids d'équivalent d'époxyde d'environ 180 à 500, et jusqu'à 10% en poids d'un polyéthylèneglycol ayant un poids moléculaire compris entre 1000 et 3000 et présentent un indice de viscosité limite, mesuré dans le chloroforme à 20°C, de 8 à 14 ml/g.
  6. Procédé selon les revendications 1 à 5, caractérisé en ce que les acides gras utilisés en plus des copolymères acide gras-acide méthacrylique présentent un indice d'iode supérieur à 120.
  7. Procédé selon la revendication 1, caractérisé en ce que l'on utilise en même temps comme monomères pour la polymérisation en émulsion jusqu'à 10% en poids, par rapport à l'ensemble du liant, de monomères à fonctionnalité hydroxyle et/ou jusqu'à 2% en poids, par rapport à l'ensemble du liant, de monomères à fonctionnalité carboxyle.
  8. Procédé selon les revendications 1 à 7, caractérisé en ce que l'on ajoute à la charge de polymérisation, de manière dosée, une partie de la résine émulsifiante en même temps que le mélange de monomères.
  9. Utilisation des émulsions préparées selon les revendications 1 à 8 comme liants pour peintures diluables à l'eau et séchant à l'air de manière oxydative à des températures atteignant 100°C.
EP19870116502 1986-11-14 1987-11-09 Préparation de liant pour peinture diluable dans l'eau et séchable à l'air Expired - Lifetime EP0267562B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT3029/86 1986-11-14
AT302986A AT387971B (de) 1986-11-14 1986-11-14 Verfahren zur herstellung wasserverduennbarer lufttrocknender lackbindemittel und deren verwendung

Publications (3)

Publication Number Publication Date
EP0267562A2 EP0267562A2 (fr) 1988-05-18
EP0267562A3 EP0267562A3 (en) 1990-05-16
EP0267562B1 true EP0267562B1 (fr) 1992-01-29

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EP (1) EP0267562B1 (fr)
JP (1) JP2599938B2 (fr)
AT (1) AT387971B (fr)
DE (1) DE3776493D1 (fr)
DK (1) DK172361B1 (fr)
ES (1) ES2038647T3 (fr)
HU (1) HU204872B (fr)
NO (1) NO172852C (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8119757B2 (en) 2007-06-04 2012-02-21 Cytec Surface Specialties Austria Gmbh Polysiloxane and urethane modified water-reducible alkyd resins
CN108641040A (zh) * 2018-05-18 2018-10-12 华伦纳路新材料有限公司 一种快速自然干燥的水性丙烯酸环氧改性醇酸树脂及其制备方法

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AT388921B (de) * 1987-06-17 1989-09-25 Vianova Kunstharz Ag Wasserverduennbare streichlacke auf der basis von wasserloeslichen alkydharzen
AT388381B (de) * 1987-09-03 1989-06-12 Vianova Kunstharz Ag Verfahren zur herstellung von waessrigen pfropfcopolymerisatemulsionen und verwendung der emulsionen als bindemittel fuer lufttrocknende wasserverduennbare anstrichmittel
AT390261B (de) * 1988-08-24 1990-04-10 Vianova Kunstharz Ag Verfahren zur herstellung von waessrigen, oxidativ trocknenden epoxidharzester-emulsionen und deren verwendung als bindemittel fuer luftrocknende lacke
ES2103536T3 (es) * 1993-01-21 1997-09-16 Akzo Nobel Nv Dispersiones polimeras acuosas de secado al aire.
AT400719B (de) * 1994-04-07 1996-03-25 Vianova Kunstharz Ag Verfahren zur herstellung von wasserverdünnbaren lufttrocknenden lackbindemitteln und deren verwendung
DE19639325A1 (de) * 1996-09-25 1998-03-26 Basf Coatings Ag Verfahren zur Herstellung einer wäßrigen Dispersion eines polyacrylatmodifizierten Polyurethan-Alkydharzes und die Verwendung einer solchen Dispersion
US6786417B1 (en) 1997-06-04 2004-09-07 Sony Corporation Memory card with write protection switch
JP3173438B2 (ja) 1997-06-04 2001-06-04 ソニー株式会社 メモリカード及び装着装置
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CN101652397B (zh) 2006-12-28 2013-04-03 树脂核动力工业有限公司 水性聚合物分散体
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HUT45551A (en) 1988-07-28
AT387971B (de) 1989-04-10
HU204872B (en) 1992-02-28
EP0267562A3 (en) 1990-05-16
ES2038647T3 (es) 1993-08-01
DK597987A (da) 1988-05-15
NO874584L (no) 1988-05-16
JPS63135464A (ja) 1988-06-07
DK597987D0 (da) 1987-11-13
DK172361B1 (da) 1998-04-14
NO172852C (no) 1993-09-15
NO874584D0 (no) 1987-11-03
JP2599938B2 (ja) 1997-04-16
ATA302986A (de) 1988-09-15
DE3776493D1 (de) 1992-03-12
NO172852B (no) 1993-06-07
EP0267562A2 (fr) 1988-05-18

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